CN117342912A - Method for producing BTX from aromatic-rich light pyrolysis distillate - Google Patents
Method for producing BTX from aromatic-rich light pyrolysis distillate Download PDFInfo
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- CN117342912A CN117342912A CN202210752052.9A CN202210752052A CN117342912A CN 117342912 A CN117342912 A CN 117342912A CN 202210752052 A CN202210752052 A CN 202210752052A CN 117342912 A CN117342912 A CN 117342912A
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- stage hydrogenation
- content
- hydrogenation
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- oil
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 45
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 169
- 239000007791 liquid phase Substances 0.000 claims abstract description 37
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 14
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 13
- 150000001993 dienes Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 111
- 238000006243 chemical reaction Methods 0.000 claims description 71
- 229910052739 hydrogen Inorganic materials 0.000 claims description 58
- 239000001257 hydrogen Substances 0.000 claims description 58
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 57
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 40
- 230000009467 reduction Effects 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000292 calcium oxide Substances 0.000 claims description 15
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 7
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 abstract description 29
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 107
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 90
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 86
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 85
- 239000000047 product Substances 0.000 description 76
- 239000000203 mixture Substances 0.000 description 60
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 42
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- 239000000243 solution Substances 0.000 description 39
- 239000008096 xylene Substances 0.000 description 29
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 28
- 239000012071 phase Substances 0.000 description 27
- 239000007789 gas Substances 0.000 description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 24
- 238000001035 drying Methods 0.000 description 24
- 239000007795 chemical reaction product Substances 0.000 description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 239000000843 powder Substances 0.000 description 17
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 description 13
- 229910000420 cerium oxide Inorganic materials 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002737 fuel gas Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000004408 titanium dioxide Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- -1 alcohol amine Chemical class 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 241000219782 Sesbania Species 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 7
- 229920000609 methyl cellulose Polymers 0.000 description 7
- 239000001923 methylcellulose Substances 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- 229910003296 Ni-Mo Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- CBUKMTMQECPKOM-UHFFFAOYSA-K C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(CCCCCCCCCCC)NCCN.[Na+].[Na+].[Na+] Chemical compound C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(CCCCCCCCCCC)NCCN.[Na+].[Na+].[Na+] CBUKMTMQECPKOM-UHFFFAOYSA-K 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 5
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- VZVMWWKJKOVAQJ-UHFFFAOYSA-K trisodium N'-hexadecylethane-1,2-diamine triacetate Chemical compound [Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.CCCCCCCCCCCCCCCCNCCN VZVMWWKJKOVAQJ-UHFFFAOYSA-K 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- OUQBWKJHTODQRM-UHFFFAOYSA-K [Na+].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(CCCCCCCCCCCCCCCCC)NCCN.[Na+].[Na+] Chemical compound [Na+].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(CCCCCCCCCCCCCCCCC)NCCN.[Na+].[Na+] OUQBWKJHTODQRM-UHFFFAOYSA-K 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000002352 steam pyrolysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
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Abstract
The invention provides a method for producing BTX from aromatic-rich light pyrolysis distillate, which adopts three-stage cyclic hydrogenation, wherein the first-stage hydrogenation is diene selective hydrogenation, the second-stage hydrogenation is to selectively hydrogenate polycyclic aromatic hydrocarbon, and the third-stage hydrogenation is selective hydrocracking. For the aromatic-rich light pyrolysis distillate oil with the final distillation point of 220-280 ℃, the total aromatic content is more than 90%, the yield of the total liquid phase product is more than 80%, and the BTX yield of the liquid phase product is more than 50%.
Description
Technical Field
The invention relates to the field of hydrotreating of aromatic-rich distillate oil, in particular to a method for producing BTX by aromatic-rich light pyrolysis distillate oil.
Background
The aromatic-rich pyrolysis distillate oil is a product of high-temperature condensation of raw materials and products of ethylene pyrolysis raw materials in the steam pyrolysis process, and mainly comes from a quenching oil tower kettle and a heavy fuel oil stripping tower kettle. The aromatic-rich pyrolysis distillate is a heavy distillate (higher than 205 ℃) rich in aromatic hydrocarbons (the aromatic hydrocarbon content is higher than 90%), the main components of the aromatic-rich pyrolysis distillate are monocyclic and polycyclic aromatic hydrocarbon compounds, the side chains are short, the hydrocarbon ratio is high, the heavy metal and ash content is low, and meanwhile, the oil also contains heterocyclic compounds of N, S, O and other elements.
The aromatic-rich pyrolysis distillate oil has higher yield in each distillation section at 170-300 ℃ and is secondarily super heavy colloid asphaltene component. Meanwhile, the aromatic-rich pyrolysis distillate oil has high sulfur content, high content of polycyclic aromatic hydrocarbon and high density. The primary distillation point-205 deg.c fraction has indene and its homolog as main component, the 205-225 deg.c fraction is naphthalene, the 225-245 deg.c fraction is methyl naphthalene, the 245-300 deg.c fraction is dimethyl naphthalene, the 300-360 deg.c fraction contains great amount of anthraquinone, acenaphthene, phenanthrene, etc. and the material of >360 deg.c is colloid and asphaltene with high hydrocarbon ratio. Wherein the naphthalene and the above polycyclic aromatic hydrocarbon account for more than 60 percent.
The aromatic-rich pyrolysis distillate is mainly used as a raw material for producing carbon black. There are also many industries beginning to produce aromatic hydrocarbon solvent oils from pyrolysis fuel oils, and major manufacturers are the U.S. Exxon, netherlands Shell, japan Bolus Petroleum, and so on.
The cracking C9 fraction is also an aromatic-rich cracking distillate oil, and is mainly derived from cracking gasoline C9 fraction separated after passing through a BTX tower, wherein the aromatic hydrocarbon content is up to more than 70 percent (the aromatic hydrocarbon content is more than 90 percent after dicyclopentadiene is extracted), and the aromatic hydrocarbon content accounts for 11-22 percent of the ethylene yield.
How to use the low added value aromatic-rich pyrolysis distillate is an urgent problem to be solved by petrochemical technology workers. Benzene (B), toluene (T) and xylene (X) are important basic organic chemical raw materials, are widely used for producing products such as polyester, chemical fiber and the like, are closely related to national economic development and people's clothing and eating activities, and have strong demands and rapid increment in recent years. Considering the abundant arene resources in ethylene tar and cracking C9, how to convert low-added value aromatic-rich cracking distillate oil into BTX by a catalytic conversion technology is a great opportunity and challenge.
In the field of hydrotreating of aromatic-rich distillate, the hydrotreating technology of catalytic cracking raw materials has been industrially applied since the 70 s of the 20 th century, and has been applied to many refineries for processing sulfur-containing or high sulfur crude oil. At present, a mature catalytic cracking raw material pretreatment technology is already owned, and mainly comprises the following steps: VGO Union and APCU (partial conversion hydrocracking) technology, haldor, UOP IncAroshift technology, VGO Hydrotreating technology, chevron, VGO Hydrodesulfurization technology, exxon, T-star technology, IFP, MAKfinding technology, mobil, AKZO, kellogg, etc. In order to further improve the product quality and conversion rate, the catalytic raw material hydrogenation pretreatment process is gradually changed from the traditional hydrodesulfurization refining (HDS) to the Mild Hydrocracking (MHC) to improve the denitrification, carbon residue and polycyclic aromatic hydrocarbon saturation capacity.
In summary, the prior art generally adopts the processes of hydrogenation saturation and hydrocracking, which has high hydrogen consumption for the aromatic hydrocarbon-rich pyrolysis distillate oil with the aromatic hydrocarbon content of more than 90 percent, and wastes valuable aromatic hydrocarbon resources.
Disclosure of Invention
Aiming at the problem of low BTX yield in the high value-added chemical utilization of the aromatic-rich light pyrolysis distillate in the prior art, the invention provides a novel method for producing BTX by using the aromatic-rich light pyrolysis distillate, and the BTX yield is greatly improved.
The first aspect of the invention provides a method for producing BTX from aromatic-rich light pyrolysis distillate, which adopts three-stage hydrogenation, wherein the first-stage hydrogenation is diene selective hydrogenation, the second-stage hydrogenation is polycyclic aromatic hydrocarbon selective hydrogenation, and the third-stage hydrogenation is selective hydrocracking;
the catalyst used for the third-stage hydrogenation (namely the third-stage hydrogenation catalyst) comprises the following components in percentage by weight:
a)5％～20％Ni；
b)0.01％～5.00％CeO 2 ；
c)55.00％～89.99％ZSM-5；
d) 5% -20% of binder;
wherein the reduction temperature of the TPR hydrogen atmosphere of the catalyst used in the third stage hydrogenation is lower than 420 ℃, and the dispersity of the active component Ni is more than 7.5%, preferably 9-20%.
Further, preferably, in the catalyst used in the third stage hydrogenation, the Ni content is 10 to 15 percent by weight, and the CeO content is 2 The content is 0.5-3.0%, the binder content is 8-15%, and the balance is ZSM-5.
Further, an alkaline earth metal such as calcium may be added as an anti-coking agent to the catalyst used in the third-stage hydrogenation. Preferably, the catalyst used in the third stage hydrogenation contains 0.1 to 3.0 percent of alkaline earth metal oxide, and preferably the alkaline earth metal oxide is calcium oxide and/or magnesium oxide.
Further, preferably, the temperature of the reduction in the TPR hydrogen atmosphere of the catalyst used in the third stage hydrogenation is lower than 400 ℃, more preferably, the temperature of the reduction in the TPR hydrogen atmosphere of the catalyst used in the third stage hydrogenation is lower than 390 ℃, and the dispersity of the active component Ni is higher than 10%, preferably 11 to 20%.
Further, the catalyst used in the first stage hydrogenation (i.e. the first stage hydrogenation catalyst) is a Ni-based catalyst, and the nickel content is 12% -16% based on the weight of the catalyst.
Further, the catalyst used in the second stage hydrogenation (i.e., second stage hydrogenation catalyst) comprises TiO 2 -SiO 2 -Al 2 O 3 Composite carrier and active component Mo-Ni, the content of composite carrier is 64% -90% based on catalyst weight, active component Mo is MoO 3 The content of the active component Ni is 8 to 30 percent, the content of the active component Ni is 2 to 6 percent based on NiO, and the active component Ni is Al 2 O 3 -TiO 2 -SiO 2 Al based on the total weight of the composite carrier 2 O 3 The content of (3) is 80% -98%, tiO 2 The content of (2) is 1% -10%, siO 2 The content of (2) is 1% -15%.
Further, the three-stage hydrogenation process comprises: the aromatic-rich light pyrolysis distillate oil and hydrogen are subjected to diene selective hydrogenation reaction in the presence of a first-stage hydrogenation catalyst, a product obtained by the first-stage hydrogenation is subjected to polycyclic aromatic hydrocarbon selective hydrogenation reaction in the presence of a second-stage hydrogenation catalyst, a product obtained by the second-stage hydrogenation is subjected to selective hydrocracking reaction in the presence of a third-stage hydrogenation catalyst, and a hydrocracking product obtained by the third-stage hydrogenation is separated to obtain BTX.
Further, the first stage hydrogenation is to hydrogenate diene, styrene and the like in the aromatic-rich light pyrolysis distillate oil into mono-olefins, and the bromine number of the product is less than 25gBr 2 100g of oil. The second stage hydrogenation is to remove unsaturated hydrocarbon, sulfur and nitrogen in aromatic hydrocarbon in the first stage hydrogenation product, selectively hydrogenate polycyclic aromatic hydrocarbon into tetrahydronaphthalene, wherein the polycyclic aromatic hydrocarbon content in the product is less than 2%, and the aromatic hydrocarbon retention rate is more than 93%. The third stage hydrogenation is to selectively hydrogenate the tetrahydronaphthalene in the second stage hydrogenation product, selectively ring-opening dealkylate polycyclic aromatic hydrocarbon and the like to generate BTX, wherein the yield of the total liquid phase product in the hydrocracking product is more than 80%, and the yield of the liquid phase product BTX is more than 50%.
Further, the three-stage hydrogenation preferably adopts three-stage circulation hydrogenation, namely, the first-stage hydrogenation circulation material is a product obtained by the first-stage hydrogenation, the second-stage hydrogenation circulation material is a product obtained by the second-stage hydrogenation, and the third-stage hydrogenation circulation material is a hydrocracking product obtained by the third-stage hydrogenation.
Further, the reaction conditions of the first stage hydrogenation are as follows: the inlet temperature of the reactor is 40-90 ℃, and the space velocity of fresh feed (raw material) is 0.8-2.0 h -1 The circulation ratio is 1.0:2.0-1.0:7.0, the hydrogen-oil volume ratio is 300-1000, and the pressure is 2-8 MPa.
Further, the reaction conditions of the second stage hydrogenation are as follows: the inlet temperature of the reactor is 240-350 ℃, and the space velocity of fresh feed (raw material) is 0.8-2.0 h -1 The circulation ratio is 1.0:0.3-1.0:2.0, the hydrogen oil volume ratio is 500-2000, and the pressure is 2-8 MPa.
Further, the reaction conditions of the third stage hydrogenation are as follows: the inlet temperature of the reactor is 380-480 ℃, and the space velocity of fresh feed (raw material) is 0.6-4.0 h -1 The hydrogen oil volume ratio is 500-2000, and the pressure is 2-8 MPa.
Further, the second-stage hydrogenation reaction raw material is a product obtained by the first-stage hydrogenation, and the third-stage hydrogenation reaction raw material is a product obtained by the second-stage hydrogenation.
Further, the aromatic-rich light cracked distillate oil: the initial boiling point is 85-170 ℃, the final boiling point is 220-280 ℃, and the raw materials consist of: sulfur content <600ug/mL, nitrogen content <300ug/mL; the aromatic hydrocarbon content is more than 90wt%.
The invention also provides a preparation method of the catalyst for the second-stage hydrogenation, which comprises the following steps:
impregnating TiO with an impregnating solution containing Mo-Ni 2 -SiO 2 -Al 2 O 3 And (3) drying and roasting the composite carrier to obtain the catalyst for the second stage hydrogenation.
Further, the composite carrier adopts the commercial Al 2 O 3 -TiO 2 -SiO 2 The carrier is TiO based on the weight of the composite carrier 2 The content is 1-10%, siO 2 The content is 1-15%, the rest is Al 2 O 3 。
Further, the composite carrier is subjected to activation treatment before use, and the activation conditions are as follows: roasting for 1-8 h at 400-700 ℃.
Further, the saturated water absorption of the composite carrier is 90-110%.
Further, the content of NiO in the impregnating solution is 2-15 g/100mL, and Mo is contained in the impregnating solution 2 O 3 The content of (C) is 10-30 g/100mL.
Further, the impregnation method is not particularly limited, and may be impregnation according to impregnation methods conventional in the art.
Further, the drying conditions are: the drying temperature is 50-200 ℃ and the drying time is 2-48 h.
Further, the roasting conditions are as follows: the roasting temperature is 300-600 ℃, and the roasting time is 2-24 h.
The invention also provides a preparation method of the catalyst for the third-stage hydrogenation, which comprises the following steps:
will contain CeO 2 And ZSM-5, and contacting the composite carrier with an impregnating solution containing a nickel source, a chelating surfactant and an alcohol amine for aging impregnation, first drying, first roasting and reduction.
Further, the catalyst contains CeO 2 And ZSM-5 composite carrier contains alkaline earth metal oxide, and the specific dosage is selected according to the requirement.
Further, the nickel source may be selected from a wide range of types, and preferably, the nickel source is selected from at least one of nickel nitrate, nickel acetate and basic nickel carbonate.
Further, the chelating surfactant has a wide optional range, and preferably, the chelating surfactant is an alkyl ethylenediamine triacetic surfactant; preferably, the alkyl ethylenediamine triacetic acid surfactant is selected from one or more of sodium N-dodecyl ethylenediamine triacetate, sodium N-hexadecyl ethylenediamine triacetate and sodium N-octadecyl ethylenediamine triacetate.
Further, the alcohol amine can be selected from a wide range, and preferably, the alcohol amine is one or more of triethanolamine, diethanolamine, and ethanolamine.
Further, the chelating surfactant in the impregnating solution is used in an amount of 0.02% -35% of the Ni, preferably 0.06% -35% of the Ni, and the alcohol amine is used in an amount of 0.02% -35% of the Ni, preferably 0.06% -35% of the Ni, based on the weight of Ni in the impregnating solution.
Further, there is no particular requirement on the impregnation method, and a conventional impregnation method and conditions, preferably, an isovolumetric impregnation method or a spray method may be used for impregnating the above composite support. The impregnation conditions included: the equal volume impregnation is carried out, the aging temperature is 10-80 ℃, preferably 15-30 ℃, and the aging time is 0.5-24 h.
Further, common drying conditions may be used in the present invention, and according to a preferred embodiment of the present invention, the first drying conditions include: the temperature is 30-200 ℃ and the time is 2-48 h.
Further, common firing conditions may be used in the present invention, and according to a preferred embodiment of the present invention, the first firing conditions include: the temperature is 300-600 ℃ and the time is 0.5-24 h.
Further, common reducing conditions may be used in the present invention, and according to a preferred embodiment of the present invention, the reducing conditions include: the reduction temperature is 350-550 ℃ and the time is 24-100 h.
Further, the catalyst contains CeO 2 The preparation method of the ZSM-5 composite carrier comprises the following steps: mixing ZSM-5 powder, optional alkaline earth metal source, cerium source, binder source, optional auxiliary agent source and acid liquor, kneading, forming, secondary drying and secondary roasting.
Further, preferably, the catalyst contains CeO 2 The preparation method of the ZSM-5 composite carrier comprises the following steps: mixing an adhesive source, ZSM-5 powder and optional auxiliary agent to obtain a first mixture, and then mixing and contacting the first mixture with an acid solution containing a cerium source and optional alkaline earth metal source for kneading, forming, drying for the second time and roasting for the second time; preferably, the weight ratio of the first mixture to the acid liquor is 100:5-100:100.
Further, the ZSM-5 powder is in a hydrogen form, siO 2 /Al 2 O 3 The molar ratio is 50 to 500, preferably 50And more preferably from 100 to 250.
Further, the binder source is selected from at least one of silica sol, water glass, pseudo-boehmite, white carbon black and alumina sol, preferably at least one of pseudo-boehmite, water glass and silica sol.
Further, the auxiliary source is selected from at least one of methylcellulose, sesbania powder, polyethylene glycol, calcium nitrate, magnesium nitrate and hydroxymethyl cellulose.
Further, the acid substance of the acid solution is at least one selected from nitric acid, phosphoric acid, acetic acid, citric acid and tartaric acid.
Further, the acid solution is an acidic aqueous solution with a concentration of 1 to 6 weight percent. This can improve the hydrocracking selective hydrogenation effect.
Further, the alkaline earth metal source is not particularly limited, and may be, for example, a commonly used alkaline earth metal compound, for example, calcium nitrate when the alkaline earth metal is calcium, which is merely an exemplary illustration, and thus does not limit the scope of the present invention.
Further, the drying conditions are not particularly required, and according to a preferred embodiment of the present invention, the second drying conditions include: drying at 50-200 deg.c for 3-48 hr, preferably at 60-120 deg.c for 5-12 hr. The conditions of firing are not particularly limited, and according to a preferred embodiment of the present invention, the conditions of the second firing include: roasting for 0.5-24 h at 450-750 ℃, preferably for 1-24 h at 480-650 ℃.
Compared with the prior art, the invention has the beneficial effects that:
According to the method for producing BTX by using the aromatic-rich light pyrolysis distillate oil, three-stage cyclic hydrogenation is adopted, the first-stage hydrogenation is diene selective hydrogenation, the second-stage hydrogenation is polycyclic aromatic hydrocarbon selective hydrogenation, and the third-stage hydrogenation is selective hydrocracking, wherein a chelating surfactant, such as an alkyl ethylenediamine triacetic acid surfactant and an alcohol amine organic compound, is added into a catalyst used in the third-stage hydrogenation in a preparation process, the reduction temperature of the catalyst TPR in a hydrogen atmosphere is reduced, and cerium oxide is added into a carrier, so that the BTX yield is improved.
The method for producing BTX by the aromatic-rich light pyrolysis distillate oil well solves the problem that the aromatic-rich light pyrolysis distillate oil cannot be directly utilized, enables the aromatic-rich light pyrolysis distillate oil with low added value to be efficiently converted into BTX with high added value, enables the initial distillation point to be 85-170 ℃, the final distillation point to be 220-280 ℃, enables the total aromatic hydrocarbon content to be more than 90% of the aromatic-rich light pyrolysis distillate oil, enables the yield of the total liquid phase product to be more than 80%, enables the yield of the liquid phase product BTX to be more than 50%, and achieves good technical effects.
Drawings
FIG. 1 is a process flow of the process of producing BTX from aromatic-rich light cracked distillate of the present invention;
1-a first stage reactor; a 2-two-stage reactor; 3-three-stage reactor; 4-separator 1; 5-separator 2; 6-separator 3; 7-a benzene removal tower; 8-toluene column; 9-xylene column; 10-aromatic-rich light cracked distillate; 11-solvent oil; 12-H 2 +CH 4 The method comprises the steps of carrying out a first treatment on the surface of the 13-C2-C4 alkane; 14-benzene; 15-toluene; 16-C8 aromatics; 17-weight material; 18-raffinate;
FIG. 2 is a graph of the distribution of the material versus the on-line time for example 1 of the present invention;
FIG. 3 is an XRD pattern of the catalyst used in the third stage of hydrogenation according to example 1 of the present invention;
FIG. 4 is a temperature programmed reduction TPR map of the catalyst used in the third stage hydrogenation of example 1 of the present invention;
FIG. 5 is a graph of product distribution versus on-line time for comparative example 1 of the present invention;
FIG. 6 is a temperature programmed reduction TPR spectrum of the catalyst for the third stage hydrogenation according to comparative example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the specific embodiments.
In the invention, the aromatic-rich light pyrolysis distillate oil (10) is subjected to one-stage reaction to remove diene in the raw material, and partial circulation is adopted to reduce reaction temperature rise due to large reaction heat release, namely, partial one-stage reaction products are returned to a one-stage reactor inlet to be mixed with the raw material and then enter the reactor (1); the other part of the first-stage reaction product enters a second-stage reactor (2), and the second-stage reaction is mainly the selectivity of the polycyclic aromatic hydrocarbonThe hydrogenation, desulfurization, denitrification and other reactions, the great heat release amount is needed to adopt partial circulation to reduce the reaction temperature rise, namely, part of the second-stage reaction products flow back to the inlet of the second-stage reactor and are mixed with the second-stage raw materials and then enter the second-stage reactor (2), and the other part of the second-stage reaction products enter the third-stage reactor (3); the three-stage reaction mainly comprises hydrocracking, dealkylation and transalkylation, the reaction product is separated into liquid phase and gas phase by a separator (4), and the gas phase product is separated into H by a separator (5) 2 +CH 4 (12) Separating a C2-C4 (13) gas-phase product and a tank bottom residual liquid (18) from a tank substrate through a separator (6); the liquid phase product separated by the separator (4) is separated into benzene by a benzene removal tower (7); the tower bottom enters a toluene tower (8) to separate toluene; the toluene tower bottom enters a xylene tower (9) to separate out the xylene, the tower bottom is recycled to a three-way inlet to be mixed with three-section raw materials and then enters a reactor (3), and part of the heavy materials (17) at the bottom of the xylene tower are discharged outside the boundary, so that the accumulation of the heavy materials in the system is prevented.
In the invention, the dispersity test method of the active component Ni is an oxyhydrogen titration method.
Wherein: dispersity of R- - - -Ni;
[ Ni ] - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -;
[Ni] total (S) -total nickel atom number;
V 0 -titration amount of hydrogen, mL;
N A -Avgalileo constant (6.023). Times.10 23 ；
W- -pattern mass, g;
p- -the mass fraction of nickel in the form,%;
m- -atomic weight of nickel 58.7.
In the invention, the test method of TPR hydrogen atmosphere reduction is an oxyhydrogen titration method.
In the invention, the liquid phase product yield is calculated by the following steps:
liquid phase product yield = W Liquid product /W Raw materials ，
W Liquid product -weight of liquid phase reaction product in line 24 hours, grams;
W raw materials -feed of aromatic-rich light cracked distillate feedstock in line for 24 hours, grams.
In the invention, the temperature of the active component Ni reduction peak is measured by adopting a TPR temperature programming reduction method, hydrogen atmosphere is adopted for reduction, the temperature rising rate is 10 ℃/min, and the temperature is increased to 900 ℃.
[ example 1 ]
Takes aromatic-rich pyrolysis oil with initial distillation point of 165 ℃ and final distillation point of 260 ℃ as raw material, and bromine valence of 65gBr 2 Per 100g of oil, aromatic hydrocarbon content of more than 98%, sulfur of 120ug/mL and nitrogen of 42ug/mL, and producing BTX by adopting a three-stage circulating hydrogenation process flow (figure 1); the first stage hydrogenation adopts Ni/Al containing 13% of nickel 2 O 3 Catalyst, reactor (1 reaction) inlet temperature 45 ℃, pressure 6.0MPa, fresh feed space velocity 1.0h -1 The hydrogen oil volume ratio was 500, the fresh oil to recycle product volume ratio was 1.0:5.0, and the reaction conditions and product data are shown in Table 1.
The second stage hydrogenation adopts Ni-Mo/TiO 2 -SiO 2 -Al 2 O 3 Catalyst, reactor (2 reaction) inlet temperature 280 ℃, pressure 5.5MPa, fresh feed space velocity 0.8h -1 The hydrogen oil volume ratio 1200, the fresh oil to product volume ratio for recycle 1.0:0.5, the reaction process conditions and the product composition data are shown in tables 2 and 3. The catalyst composition used for the second stage hydrogenation is as follows: tiO (titanium dioxide) 2 -SiO 2 -Al 2 O 3 The content is 78% (TiO) 2 8.5% of SiO 2 9.5% of Al 2 O 3 82 percent of NiO content is 9 percent, moO 3 The content was 13%.
The inlet temperature of the third-stage hydrogenation reactor (3 reverse) is 420 ℃, the pressure is 5.0MPa, and the space velocity of fresh feed is 0.8h -1 The material at the reverse outlet of the hydrogen-oil volume ratio 1500,3 is separated into two materials of gas phase and liquid phase by a separator 1, and the gas phase material is respectively generated into fuel gas, C2-C4 alkane and a small amount of residual liquid by a separator 2 and a separator 3; the liquid phase material generated by the separator 1 is respectively processed by a benzene removal tower, a toluene tower and a xylene tower to obtain pure benzene,Toluene and mixed C8 aromatic hydrocarbon, the bottom of the xylene tower is recycled to the 3-reverse inlet, part of heavy components are discharged out of the system, the reaction process conditions are shown in Table 4, and the composition data of reaction products are shown in Table 5 and FIG. 2. The composition of the catalyst used for three-stage hydrogenation is as follows: the Ni content of the active component is 15 percent, and the balance is the composite carrier.
The preparation method of the catalyst used for the third-stage hydrogenation comprises the following steps:
selecting hydrogen type SiO 2 /Al 2 O 3 832 g of ZSM-5 molecular sieve powder (dried before use) which is 150 g of pseudo-boehmite calculated by 150 g of alumina, 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 8 g of cerium oxide and calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the above-mentioned mixed powder, kneading for 35 min, extruding to form strips, placing at 20 deg.C for 12 hr, drying at 110 deg.C for 6 hr, placing into a muffle furnace, roasting at 600 deg.C for 5 hr so as to obtain the invented composite carrier (the weight percentage composition of composite carrier: ZSM-5 content 83.2% and Al) 2 O 3 15% of calcium oxide, 1% of cerium oxide, 0.8% of cerium oxide, and the water absorption rate is 102%.
Preparing an impregnating solution containing 30 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, adding 1 g of N-dodecyl ethylenediamine sodium triacetate and 1 g of triethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the same volume of the impregnating solution on the composite carrier by adopting a rotary pot spraying method, ageing for 16 hours at 25 ℃, drying for 4 hours at 100 ℃, roasting for 4 hours at 400 ℃, and obtaining the oxidation catalyst, and reducing for 48 hours in a hydrogen atmosphere at 350 ℃ to obtain the reduction catalyst. The XRD patterns of the hydrogen ZSM-5 powder, the composite carrier and the catalyst are shown in figure 3, the temperature programming reduction TPR pattern of the oxidative catalyst is shown in figure 4, and the peak value of the reduction temperature of the active component in the hydrogen atmosphere is 377 ℃ according to figure 4, so that the active component is well dispersed, easy to reduce and high in activity. The dispersity of the reduced catalyst Ni was 16.3%.
[ example 2 ]
Aromatic-rich cracking with initial distillation point of 165 ℃ and final distillation point of 260 DEG CThe de-oiling is used as raw material, the bromine valence is 65gBr 2 Per 100g of oil, aromatic hydrocarbon content of more than 98%, sulfur of 120ug/mL and nitrogen of 42ug/mL, and producing BTX by adopting a three-stage circulating hydrogenation process flow (figure 1); the first stage hydrogenation adopts Ni/Al containing 13% of nickel 2 O 3 Catalyst, reactor (1 reaction) inlet temperature 45 ℃, fresh feed space velocity 1.0h -1 The volume ratio of fresh oil to product for recycle is 1.0:5.0, the volume ratio of hydrogen oil is 500, the pressure is 6.0MPa, and the reaction conditions and product data are shown in Table 1.
The inlet temperature of the second-stage hydrogenation reactor (2 reverse) is 280 ℃, the pressure is 5.5MPa, and the space velocity of fresh feed is 0.8h -1 The hydrogen oil volume ratio 1200, the fresh oil to product volume ratio for recycle 1.0:0.5, the reaction process conditions and the product composition data are shown in tables 2 and 3. The catalyst composition used for the second stage hydrogenation is as follows: tiO (titanium dioxide) 2 -SiO 2 -Al 2 O 3 The content is 78% (TiO) 2 8.5% of SiO 2 9.5% of Al 2 O 3 82 percent of NiO content is 9 percent, moO 3 The content was 13%.
The inlet temperature of the third-stage hydrogenation reactor (3 reverse) is 450 ℃, the pressure is 6.5MPa, and the space velocity of fresh feed is 1.2h -1 Separating the hydrogen-oil volume ratio 800,3 back-outlet material into gas phase and liquid phase two materials by a separator 1, and generating fuel gas, C2-C4 alkane and a small amount of residual liquid by the gas phase material by a separator 2 and a separator 3; the liquid phase material generated by the separator 1 is respectively subjected to a benzene removal tower, a toluene tower and a xylene tower to obtain pure benzene, toluene and mixed C8 aromatic hydrocarbon, the xylene tower substrate is circulated to a 3-reverse inlet, part of heavy components are discharged out of the system, the reaction process conditions are shown in Table 4, and the composition data of the reaction products are shown in Table 5. The catalyst composition used for the third stage hydrogenation is as follows: the Ni content of the active component is 15 percent, and the balance is the composite carrier.
The preparation method of the catalyst used for the third-stage hydrogenation comprises the following steps:
selecting hydrogen type SiO 2 /Al 2 O 3 840 g of ZSM-5 molecular sieve powder (dried before use), 15 g of methylcellulose and sesbania powder respectively, which are evenly mixed for standby, wherein the silica sol is calculated by 145 g of silicon dioxide; then adding 8 g of nitric acid and 5 g of citric acid into 550 g of water to be uniformly dissolved, and thenAdding cerium nitrate containing 5 g cerium oxide and calcium nitrate containing 10 g calcium oxide, dissolving uniformly, pouring the solution into the above mixed powder, kneading for 35 min, extruding to form, standing at 20deg.C for 12 hr, drying at 110deg.C for 6 hr, and calcining at 600deg.C for 4 hr to obtain composite carrier (composite carrier weight percentage composition: ZSM-5 content 84%, siO) 2 (binder) content 14.5%, calcium oxide content 1.0%, cerium oxide content 0.5%) and water absorption 103%.
Preparing an impregnating solution containing 30 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 170 ml, adding 0.02 g of N-hexadecyl ethylenediamine sodium triacetate and 8 g of ethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a rotary pot spraying method, ageing for 16 hours at 25 ℃, drying for 4 hours at 100 ℃, roasting for 4 hours at 400 ℃, obtaining an oxidation catalyst, reducing for 42 hours in a hydrogen atmosphere at 400 ℃, obtaining a reduction catalyst, wherein the dispersity of Ni of the reduction catalyst is 15.8%, and the temperature of a TPR programmed heating reduction peak of the oxidation catalyst is 380 ℃.
[ example 3 ]
Takes aromatic-rich pyrolysis oil with initial distillation point of 165 ℃ and final distillation point of 260 ℃ as raw material, and bromine valence of 65gBr 2 Per 100g of oil, aromatic hydrocarbon content of more than 98%, sulfur of 120ug/mL and nitrogen of 42ug/mL, and producing BTX by adopting a three-stage circulating hydrogenation process flow (figure 1); the first stage hydrogenation adopts Ni/Al containing 13% of nickel 2 O 3 Catalyst, reactor (1 reaction) inlet temperature 45 ℃, fresh feed space velocity 1.0h -1 The volume ratio of fresh oil to product for recycle is 1.0:5.0, the volume ratio of hydrogen oil is 500, the pressure is 6.0MPa, and the reaction conditions and product data are shown in Table 1.
The inlet temperature of the second-stage hydrogenation reactor (2 reverse) is 280 ℃, the pressure is 5.5MPa, and the space velocity of fresh feed is 0.8h -1 The hydrogen oil volume ratio 1200, the fresh oil to product volume ratio for recycle 1.0:0.5, the reaction process conditions and the product composition data are shown in tables 2 and 3. The catalyst composition used for the second stage hydrogenation is as follows: tiO (titanium dioxide) 2 -SiO 2 -Al 2 O 3 The content is 78% (TiO) 2 8.5% of SiO 2 9.5% of Al 2 O 3 82 percent of NiO content is 9 percent, moO 3 The content was 13%.
The inlet temperature of the third-stage hydrogenation reactor (3 reverse) is 410 ℃, the pressure is 5.5MPa, and the space velocity of fresh feed is 1.0h -1 Separating the hydrogen-oil volume ratio 1500,3 back-outlet material into gas phase and liquid phase two materials by a separator 1, and generating fuel gas, C2-C4 alkane and a small amount of residual liquid by the gas phase material by a separator 2 and a separator 3; the liquid phase material generated by the separator 1 is respectively subjected to a benzene removal tower, a toluene tower and a xylene tower to obtain pure benzene, toluene and mixed C8 aromatic hydrocarbon, the xylene tower substrate is circulated to a 3-reverse inlet, part of heavy components are discharged out of the system, the reaction process conditions are shown in Table 4, and the composition data of the reaction products are shown in Table 5. The catalyst composition used for the third stage hydrogenation is as follows: the Ni content of the active component is 15 percent, and the balance is the composite carrier.
The catalyst used in the third stage hydrogenation was prepared in the same manner as described in example 1.
[ example 4 ]
Takes aromatic-rich pyrolysis oil with initial distillation point of 165 ℃ and final distillation point of 260 ℃ as raw material, and bromine valence of 65gBr 2 Per 100g of oil, aromatic hydrocarbon content of more than 98%, sulfur of 120ug/mL and nitrogen of 42ug/mL, and producing BTX by adopting a three-stage circulating hydrogenation process flow (figure 1); the first stage hydrogenation adopts Ni/Al containing 13% of nickel 2 O 3 Catalyst, reactor (1 reaction) inlet temperature 45 ℃, fresh feed space velocity 1.0h -1 The volume ratio of fresh oil to product for recycle is 1.0:5.0, the volume ratio of hydrogen oil is 500, the pressure is 6.0MPa, and the reaction conditions and product data are shown in Table 1.
The inlet temperature of the second-stage hydrogenation reactor (2 reverse) is 280 ℃, the pressure is 5.5MPa, and the space velocity of fresh feed is 0.8h -1 The hydrogen oil volume ratio 1200, the fresh oil to product volume ratio for recycle 1.0:0.5, the reaction process conditions and the product composition data are shown in tables 2 and 3. The catalyst composition used for the second stage hydrogenation is as follows: tiO (titanium dioxide) 2 -SiO 2 -Al 2 O 3 The content is 78% (TiO) 2 8.5% of SiO 2 9.5% of Al 2 O 3 82 percent of NiO content is 9 percent, moO 3 The content was 13%.
Third stage hydrogenation reactionThe inlet temperature of the reactor (3 reverse) is 410 ℃, the pressure is 5.5MPa, and the space velocity of fresh feed is 1.0h -1 Separating the hydrogen-oil volume ratio 1800,3 back-outlet material into gas phase and liquid phase two materials by a separator 1, and generating fuel gas, C2-C4 alkane and a small amount of residual liquid by the gas phase material by a separator 2 and a separator 3; the liquid phase material generated by the separator 1 is respectively subjected to a benzene removal tower, a toluene tower and a xylene tower to obtain pure benzene, toluene and mixed C8 aromatic hydrocarbon, the xylene tower substrate is circulated to a 3-reverse inlet, part of heavy components are discharged out of the system, the reaction process conditions are shown in Table 4, and the composition data of the reaction products are shown in Table 5. The catalyst composition used for the third stage hydrogenation is as follows: the Ni content of the active component is 15 percent, and the balance is the composite carrier.
The catalyst used in the third stage hydrogenation was prepared in the same manner as described in example 1.
[ example 5 ]
Takes aromatic-rich pyrolysis oil with initial distillation point of 165 ℃ and final distillation point of 260 ℃ as raw material, and bromine valence of 65gBr 2 Per 100g of oil, aromatic hydrocarbon content of more than 98%, sulfur of 120ug/mL and nitrogen of 42ug/mL, and producing BTX by adopting a three-stage circulating hydrogenation process flow (figure 1); the first stage hydrogenation adopts Ni/Al containing 13% of nickel 2 O 3 Catalyst, reactor (1 reaction) inlet temperature 45 ℃, fresh feed space velocity 1.0h -1 The volume ratio of fresh oil to product for recycle is 1.0:5.0, the volume ratio of hydrogen oil is 500, the pressure is 6.0MPa, and the reaction conditions and product data are shown in Table 1.
The inlet temperature of the second-stage hydrogenation reactor (2 reverse) is 280 ℃, the pressure is 5.5MPa, and the space velocity of fresh feed is 0.8h -1 The hydrogen oil volume ratio 1200, the fresh oil to product volume ratio for recycle 1.0:0.5, the reaction process conditions and the product composition data are shown in tables 2 and 3. The catalyst composition used for the second stage hydrogenation is as follows: tiO (titanium dioxide) 2 -SiO 2 -Al 2 O 3 The content is 78% (TiO) 2 8.5% of SiO 2 9.5% of Al 2 O 3 82 percent of NiO content is 9 percent, moO 3 The content was 13%.
The inlet temperature of the third-stage hydrogenation reactor (3 reverse) is 470 ℃, the pressure is 6.0MPa, and the space velocity of fresh feed is 2.0h -1 The hydrogen-oil volume ratio 2000,3 reverse outlet material is separated into two materials of gas phase and liquid phase by a separator 1 The gas phase material passes through a separator 2 and a separator 3 to generate fuel gas, C2-C4 alkane and a small amount of residual liquid; the liquid phase material generated by the separator 1 is respectively subjected to a benzene removal tower, a toluene tower and a xylene tower to obtain pure benzene, toluene and mixed C8 aromatic hydrocarbon, the xylene tower substrate is circulated to a 3-reverse inlet, part of heavy components are discharged out of the system, the reaction process conditions are shown in Table 4, and the composition data of the reaction products are shown in Table 5. The catalyst composition used for the third stage hydrogenation is as follows: the Ni content of the active component is 15 percent, and the balance is the composite carrier.
The third stage hydrogenation catalyst preparation process is the same as in example 1.
[ example 6 ]
Takes aromatic-rich pyrolysis oil with initial distillation point of 165 ℃ and final distillation point of 260 ℃ as raw material, and bromine valence of 65gBr 2 Per 100g of oil, aromatic hydrocarbon content of more than 98%, sulfur of 120ug/mL and nitrogen of 42ug/mL, and producing BTX by adopting a three-stage circulating hydrogenation process flow (figure 1); the first stage hydrogenation adopts Ni/Al containing 13% of nickel 2 O 3 Catalyst, reactor (1 reaction) inlet temperature 50 ℃, pressure 5.5MPa, fresh feed space velocity 1.2h -1 The volume ratio of fresh oil to product for recycle is 1.0:4.0, the volume ratio of hydrogen oil is 800, and the reaction process conditions and product composition data are shown in Table 1.
The inlet temperature of the second-stage hydrogenation reactor (2 reverse) is 290 ℃, the pressure is 5.0MPa, and the space velocity of fresh feed is 1.0h -1 The hydrogen oil volume ratio 1500, the fresh oil to product volume ratio for recycle 1.0:1.0, the reaction process conditions and the product composition data are shown in tables 2 and 3. The catalyst composition used for the second stage hydrogenation is as follows: tiO (titanium dioxide) 2 -SiO 2 -Al 2 O 3 The content is 78% (TiO) 2 8.5% of SiO 2 9.5% of Al 2 O 3 82 percent of NiO content is 9 percent, moO 3 The content was 13%.
The inlet temperature of the third-stage hydrogenation reactor (3 reverse) is 470 ℃, the pressure is 6.0MPa, and the space velocity of fresh feed is 2.0h -1 Separating the hydrogen-oil volume ratio 2000,3 back-outlet material into gas phase and liquid phase two materials by a separator 1, and generating fuel gas, C2-C4 alkane and a small amount of residual liquid by the gas phase material by a separator 2 and a separator 3; the liquid phase material generated by the separator 1 is processed by a benzene removal tower, a toluene tower and a xylene towerPure benzene, toluene and mixed C8 aromatic hydrocarbon are respectively obtained, the bottom of the xylene tower is circulated to the 3-reverse inlet, partial heavy components are discharged out of the system, the reaction process conditions are shown in Table 4, and the composition data of the reaction products are shown in Table 5. The catalyst composition used for the third stage hydrogenation is as follows: the Ni content of the active component is 15 percent, and the balance is the composite carrier.
The preparation method of the catalyst used for the third-stage hydrogenation comprises the following steps:
selecting hydrogen type SiO 2 /Al 2 O 3 820 g of ZSM-5 molecular sieve powder (dried before use) which is prepared by uniformly mixing 15 g of pseudo-boehmite, methylcellulose and sesbania powder which are calculated by 145 g of alumina; then adding 13 g of nitric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 20 g of cerium oxide and calcium nitrate containing 15 g of calcium oxide to dissolve uniformly, pouring the solution into the above-mentioned mixed powder body, kneading for 35 min, extruding and forming, placing at 20 deg.C for 12 hr, drying at 110 deg.C for 6 hr, placing into a muffle furnace and roasting at 550 deg.C for 6 hr so as to obtain the invented composite carrier (ZSM-5 content is 82% by weight and Al content is 82% by weight) 2 O 3 14.5%, 1.5% calcium oxide and 2.0% cerium oxide, and the water absorption rate is 105%.
Preparing an impregnating solution containing 40 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 160 ml, adding 1 g of N-dodecyl ethylenediamine sodium triacetate, 0.8 g of ethanolamine and 0.8 g of triethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 160 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume by adopting a rotary pot spraying method, ageing for 16 hours at 20 ℃, drying for 3 hours at 180 ℃, roasting for 2 hours at 600 ℃, obtaining an oxidation catalyst, reducing for 40 hours in a hydrogen atmosphere at 450 ℃, and obtaining a reduction catalyst, wherein the dispersity of Ni of the reduction catalyst is 15.2%. The temperature programmed reduction peak temperature of the TPR of the oxidative catalyst was 389 ℃.
[ example 7 ]
Takes aromatic-rich pyrolysis oil with initial distillation point of 165 ℃ and final distillation point of 260 ℃ as raw material, and bromine valence of 65gBr 2 100g of oil, aromatic hydrocarbon content of more than 98%, sulfur of 120ug/mL and nitrogen of 42ug/mL, and adopting a three-stage circulation hydrogenation process flow (figure 1)Producing BTX; the first stage adopts Ni/Al containing 13% of nickel 2 O 3 Catalyst, reactor (1 reaction) inlet temperature 50 ℃, pressure 5.5MPa, fresh feed space velocity 1.2h -1 The volume ratio of fresh oil to product for recycle is 1.0:4.0, the volume ratio of hydrogen oil is 800, and the reaction process conditions and product composition data are shown in Table 1.
The inlet temperature of the second-stage hydrogenation reactor (2 reverse) is 290 ℃, the pressure is 5.0MPa, and the space velocity of fresh feed is 1.0h -1 The hydrogen oil volume ratio 1500, the fresh oil to product volume ratio for recycle 1.0:1.0, the reaction process conditions and the product composition data are shown in tables 2 and 3. The catalyst composition used for the second stage hydrogenation is as follows: tiO (titanium dioxide) 2 -SiO 2 -Al 2 O 3 The content is 78% (TiO) 2 8.5% of SiO 2 9.5% of Al 2 O 3 82 percent of NiO content is 9 percent, moO 3 The content was 13%.
The inlet temperature of the third-stage hydrogenation reactor (3 reverse) is 410 ℃, the pressure is 5.5MPa, and the space velocity of fresh feed is 1.0h -1 Separating the hydrogen-oil volume ratio 1800,3 back-outlet material into gas phase and liquid phase two materials by a separator 1, and generating fuel gas, C2-C4 alkane and a small amount of residual liquid by the gas phase material by a separator 2 and a separator 3; the liquid phase material generated by the separator 1 is respectively subjected to a benzene removal tower, a toluene tower and a xylene tower to obtain pure benzene, toluene and mixed C8 aromatic hydrocarbon, the xylene tower substrate is circulated to a 3-reverse inlet, part of heavy components are discharged out of the system, the reaction process conditions are shown in Table 4, and the composition data of the reaction products are shown in Table 5. The catalyst composition used for the third stage hydrogenation is as follows: the Ni content of the active component is 15 percent, and the balance is the composite carrier.
The catalyst used in the third stage hydrogenation was prepared in the same manner as described in example 1.
[ example 8 ]
Takes aromatic-rich pyrolysis oil with initial distillation point of 165 ℃ and final distillation point of 260 ℃ as raw material, and bromine valence of 65gBr 2 Per 100g of oil, aromatic hydrocarbon content of more than 98%, sulfur of 120ug/mL and nitrogen of 42ug/mL, and producing BTX by adopting a three-stage circulating hydrogenation process flow (figure 1); the first stage hydrogenation adopts Ni/Al containing 13% of nickel 2 O 3 Catalyst, reactor (1 reaction) inlet temperature 50 ℃, pressure 5.5MPa, fresh feed space velocity 1.2h -1 The volume ratio of fresh oil to product for recycle is 1.0:4.0, the volume ratio of hydrogen oil is 800, and the reaction process conditions and product composition data are shown in Table 1.
The second stage hydrogenation adopts Ni-Mo/TiO 2 -SiO 2 -Al 2 O 3 Catalyst, reactor (2 reaction) inlet temperature 290 ℃, pressure 5.0MPa and fresh feed space velocity 1.0h -1 The hydrogen oil volume ratio 1500, the fresh oil to product volume ratio for recycle 1.0:1.0, the reaction process conditions and the product composition data are shown in tables 2 and 3. The catalyst composition used for the second stage hydrogenation is as follows: tiO (titanium dioxide) 2 -SiO 2 -Al 2 O 3 The content is 78% (TiO) 2 8.5% of SiO 2 9.5% of Al 2 O 3 82 percent of NiO content is 9 percent, moO 3 The content was 13%.
The inlet temperature of the third-stage hydrogenation reactor (3 reverse) is 450 ℃, the pressure is 6.5MPa, and the space velocity of fresh feed is 1.2h -1 Separating the hydrogen-oil volume ratio 1000,3 back-outlet material into gas phase and liquid phase two materials by a separator 1, and generating fuel gas, C2-C4 alkane and a small amount of residual liquid by the gas phase material by a separator 2 and a separator 3; the liquid phase material generated by the separator 1 is respectively subjected to a benzene removal tower, a toluene tower and a xylene tower to obtain pure benzene, toluene and mixed C8 aromatic hydrocarbon, the xylene tower substrate is circulated to a 3-reverse inlet, part of heavy components are discharged out of the system, the reaction process conditions are shown in Table 4, and the composition data of the reaction products are shown in Table 5. The catalyst composition used for the third stage hydrogenation is as follows: the Ni content of the active component is 15 percent, and the balance is the composite carrier.
The catalyst used in the third stage hydrogenation was prepared in the same manner as described in example 1.
[ example 9 ]
Takes aromatic-rich pyrolysis oil with initial distillation point of 165 ℃ and final distillation point of 260 ℃ as raw material, and bromine valence of 65gBr 2 Per 100g of oil, aromatic hydrocarbon content of more than 98%, sulfur of 120ug/mL and nitrogen of 42ug/mL, and producing BTX by adopting a three-stage circulating hydrogenation process flow (figure 1); the first stage hydrogenation adopts Ni/Al containing 13% of nickel 2 O 3 Catalyst, reactor (1 reaction) inlet temperature 50 ℃, pressure 5.5MPa, fresh feed space velocity 1.2h -1 The volume ratio of fresh oil to product for recycle is 1.0:4.0, hydrogen oil bodiesThe product ratio was 800, and the reaction process conditions and the product composition data are shown in Table 1.
The second stage hydrogenation adopts Ni-Mo/TiO 2 -SiO 2 -Al 2 O 3 Catalyst, reactor (2 reaction) inlet temperature 290 ℃, pressure 5.0MPa and fresh feed space velocity 1.0h -1 The hydrogen oil volume ratio 1500, the fresh oil to product volume ratio for recycle 1.0:1.0, the reaction process conditions and the product composition data are shown in tables 2 and 3. The catalyst composition used for the second stage hydrogenation is as follows: tiO (titanium dioxide) 2 -SiO 2 -Al 2 O 3 The content is 78% (TiO) 2 8.5% of SiO 2 9.5% of Al 2 O 3 82 percent of NiO content is 9 percent, moO 3 The content was 13%.
The inlet temperature of the third-stage hydrogenation reactor (3 reverse) is 420 ℃, the pressure is 5.0MPa, and the space velocity of fresh feed is 0.8h -1 Separating the hydrogen-oil volume ratio 1500,3 back-outlet material into gas phase and liquid phase two materials by a separator 1, and generating fuel gas, C2-C4 alkane and a small amount of residual liquid by the gas phase material by a separator 2 and a separator 3; the liquid phase material generated by the separator 1 is respectively subjected to a benzene removal tower, a toluene tower and a xylene tower to obtain pure benzene, toluene and mixed C8 aromatic hydrocarbon, the xylene tower substrate is circulated to a 3-reverse inlet, part of heavy components are discharged out of the system, the reaction process conditions are shown in Table 4, and the composition data of the reaction products are shown in Table 5. The catalyst composition used for the third stage hydrogenation is as follows: the Ni content of the active component is 15 percent, and the balance is the composite carrier.
The catalyst used in the third stage hydrogenation was prepared in the same manner as described in example 1.
[ example 10 ]
Takes aromatic-rich pyrolysis oil with initial distillation point of 165 ℃ and final distillation point of 260 ℃ as raw material, and bromine valence of 65gBr 2 Per 100g of oil, aromatic hydrocarbon content of more than 98%, sulfur of 120ug/mL and nitrogen of 42ug/mL, and producing BTX by adopting a three-stage circulating hydrogenation process flow (figure 1); the first stage hydrogenation adopts Ni/Al containing 13% of nickel 2 O 3 Catalyst, reactor (1 reaction) inlet temperature 45 ℃, pressure 6.0MPa, fresh feed space velocity 1.0h -1 The hydrogen oil volume ratio was 500, the fresh oil to product volume ratio for recycle was 1.0:5.0, and the reaction conditions and product data are shown in Table 1.
The second stage hydrogenation adopts Ni-Mo/TiO 2 -SiO 2 -Al 2 O 3 Catalyst, reactor (2 reaction) inlet temperature 280 ℃, pressure 5.5MPa, fresh feed space velocity 0.8h -1 The hydrogen oil volume ratio 1200, the fresh oil to product volume ratio for recycle 1.0:0.5, the reaction process conditions and the product composition data are shown in tables 2 and 3. The catalyst composition used for the second stage hydrogenation is as follows: tiO (titanium dioxide) 2 -SiO 2 -Al 2 O 3 The content is 78% (TiO) 2 8.5% of SiO 2 9.5% of Al 2 O 3 82 percent of NiO content is 9 percent, moO 3 The content was 13%.
The inlet temperature of the third-stage hydrogenation reactor (3 reverse) is 420 ℃, the pressure is 5.0MPa, and the space velocity of fresh feed is 0.8h -1 The material at the reverse outlet of the hydrogen-oil volume ratio 1500,3 is separated into two materials of gas phase and liquid phase by a separator 1, and the gas phase material is respectively generated into fuel gas, C2-C4 alkane and a small amount of residual liquid by a separator 2 and a separator 3; the liquid phase material generated by the separator 1 is respectively subjected to a benzene removal tower, a toluene tower and a xylene tower to obtain pure benzene, toluene and mixed C8 aromatic hydrocarbon, the xylene tower substrate is circulated to a 3-reverse inlet, part of heavy components are discharged out of the system, the reaction process conditions are shown in Table 4, and the composition data of the reaction products are shown in Table 5. The composition of the catalyst used for three-stage hydrogenation is as follows: the Ni content of the active component is 15 percent, and the balance is the composite carrier.
The preparation method of the catalyst used for the third-stage hydrogenation comprises the following steps:
hydrogen taking SiO 2 /Al 2 O 3 832 g of ZSM-5 molecular sieve powder (dried before use) with the molar ratio of 150, 15 g of pseudo-boehmite calculated by 150 g of alumina, methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 8 g of cerium oxide and calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the above-mentioned mixed powder, kneading for 35 min, extruding to form strips, placing at 20 deg.C for 12 hr, drying at 110 deg.C for 6 hr, placing into a muffle furnace, roasting at 600 deg.C for 5 hr so as to obtain the invented composite carrier (the weight percentage composition of composite carrier: ZSM-5 content 83.2% and Al) 2 O 3 Content of15%, calcium oxide content 1% and cerium oxide content 0.8%), the water absorption rate was 102%.
Preparing an impregnating solution containing 30 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 170 ml, adding 0.0085 g of N-dodecyl ethylenediamine sodium triacetate and 0.0085 g of triethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the impregnating solution on the composite carrier in equal volume by adopting a rotary pot spraying method, ageing for 16 hours at 25 ℃, drying for 4 hours at 100 ℃, roasting for 4 hours at 400 ℃, obtaining an oxidation catalyst, and reducing for 48 hours in a hydrogen atmosphere at 350 ℃ to obtain the hydrocracking catalyst. The dispersity of Ni of the reduction catalyst is 7.7 percent. The peak reduction temperature of the active component under the hydrogen atmosphere was 415 ℃.
[ comparative example 1 ]
Takes aromatic-rich pyrolysis oil with initial distillation point of 165 ℃ and final distillation point of 260 ℃ as raw material, and bromine valence of 65gBr 2 Per 100g of oil, aromatic hydrocarbon content of more than 98%, sulfur of 120ug/mL and nitrogen of 42ug/mL, and producing BTX by adopting a three-stage circulating hydrogenation process flow (figure 1); the first stage hydrogenation adopts Ni/Al containing 13% of nickel 2 O 3 Catalyst, reactor (1 reaction) inlet temperature 45 ℃, pressure 6.0MPa, fresh feed space velocity 1.0h -1 The hydrogen oil volume ratio was 500, the fresh oil to product volume ratio for recycle was 1.0:5.0, and the reaction conditions and product data are shown in Table 1.
The second stage hydrogenation adopts Ni-Mo/TiO 2 -SiO 2 -Al 2 O 3 Catalyst, reactor (2 reaction) inlet temperature 280 ℃, pressure 5.5MPa, fresh feed space velocity 0.8h -1 The hydrogen oil volume ratio 1200, the fresh oil to product volume ratio for recycle 1.0:0.5, the reaction process conditions and the product composition data are shown in tables 2 and 3. The catalyst composition used for the second stage hydrogenation is as follows: tiO (titanium dioxide) 2 -SiO 2 -Al 2 O 3 The content is 78% (TiO) 2 8.5% of SiO 2 9.5% of Al 2 O 3 82 percent of NiO content is 9 percent, moO 3 The content was 13%.
The inlet temperature of the third-stage hydrogenation reactor (3 reverse) is 420 ℃, the pressure is 5.0MPa, and the space velocity of fresh feed is 0.8h -1 Hydrogen oil volume ratio 1500,3 is reversedSeparating the port material into two materials of gas phase and liquid phase by a separator 1, and generating fuel gas, C2-C4 alkane and a small amount of residual liquid by the gas phase material by a separator 2 and a separator 3; the liquid phase material generated by the separator 1 is respectively subjected to a benzene removal tower, a toluene tower and a xylene tower to obtain pure benzene, toluene and mixed C8 aromatic hydrocarbon, the xylene tower substrate is circulated to a 3-reverse inlet, part of heavy components are discharged out of the system, the reaction process conditions are shown in Table 4, and the composition data of the reaction products are shown in Table 5. The catalyst composition used for the third stage hydrogenation is as follows: the Ni content of the active component is 15 percent, and the balance is the composite carrier.
The preparation method of the catalyst used for the third-stage hydrogenation comprises the following steps:
selecting hydrogen type SiO 2 /Al 2 O 3 832 g of ZSM-5 molecular sieve powder (dried before use) which is calculated as pseudo-boehmite containing 150 g of alumina, and 15 g of methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 8 g of cerium oxide and calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the above-mentioned mixed powder, kneading for 35 min, extruding to form strips, placing at 20 deg.C for 12 hr, drying at 110 deg.C for 6 hr, placing into a muffle furnace, roasting at 600 deg.C for 5 hr so as to obtain the invented composite carrier (the weight percentage composition of composite carrier: ZSM-5 content 83.2% and Al) 2 O 3 15% of calcium oxide, 1% of cerium oxide, 0.8% of cerium oxide, and the water absorption rate is 102%.
Preparing an impregnating solution containing 30 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, taking 170 g of composite carrier, loading the same volume of the impregnating solution on the composite carrier by adopting a rotary pot spraying method, aging for 16 hours at 25 ℃, drying for 4 hours at 100 ℃, roasting for 4 hours at 400 ℃ to obtain an oxidation catalyst, and reducing for 48 hours in a hydrogen atmosphere at 350 ℃ to obtain a reduction catalyst, wherein the dispersion degree of Ni in the reduction catalyst is 4.1%. The temperature programmed reduction TPR spectrum of the oxidative catalyst is shown in fig. 6, and the peak value of the reduction temperature of the active component in the hydrogen atmosphere is 440 ℃ as can be seen from fig. 6, which shows that the dispersion of the active component is poor, the reduction is difficult and the activity is low.
[ comparative example 2 ]
Takes aromatic-rich pyrolysis oil with initial distillation point of 165 ℃ and final distillation point of 260 ℃ as raw material, and bromine valence of 65gBr 2 Per 100g of oil, aromatic hydrocarbon content of more than 98%, sulfur of 120ug/mL and nitrogen of 42ug/mL, and producing BTX by adopting a three-stage circulating hydrogenation process flow (figure 1); the first stage hydrogenation adopts Ni/Al containing 13% of nickel 2 O 3 Catalyst, reactor (1 reaction) inlet temperature 45 ℃, pressure 6.0MPa, fresh feed space velocity 1.0h -1 The hydrogen oil volume ratio was 500, the fresh oil to product volume ratio for recycle was 1.0:5.0, and the reaction conditions and product data are shown in Table 1.
The second stage hydrogenation adopts Ni-Mo/TiO 2 -SiO 2 -Al 2 O 3 Catalyst, reactor (2 reaction) inlet temperature 280 ℃, pressure 5.5MPa, fresh feed space velocity 0.8h -1 The hydrogen oil volume ratio 1200, the fresh oil to product volume ratio for recycle 1.0:0.5, the reaction process conditions and the product composition data are shown in tables 2 and 3. The catalyst composition used for the second stage hydrogenation is as follows: tiO (titanium dioxide) 2 -SiO 2 -Al 2 O 3 The content is 78% (TiO) 2 8.5% of SiO 2 9.5% of Al 2 O 3 82 percent of NiO content is 9 percent, moO 3 The content was 13%.
The inlet temperature of the third-stage hydrogenation reactor (3 reverse) is 420 ℃, the pressure is 5.0MPa, and the space velocity of fresh feed is 0.8h -1 Separating the hydrogen-oil volume ratio 1500,3 back-outlet material into gas phase and liquid phase two materials by a separator 1, and generating fuel gas, C2-C4 alkane and a small amount of residual liquid by the gas phase material by a separator 2 and a separator 3; the liquid phase material generated by the separator 1 is respectively subjected to a benzene removal tower, a toluene tower and a xylene tower to obtain pure benzene, toluene and mixed C8 aromatic hydrocarbon, the xylene tower substrate is circulated to a 3-reverse inlet, part of heavy components are discharged out of the system, the reaction process conditions are shown in Table 4, and the composition data of the reaction products are shown in Table 5. The catalyst composition used for the third stage hydrogenation is as follows: the Ni content of the active component is 15 percent, and the balance is the composite carrier.
The preparation method of the catalyst used for the third-stage hydrogenation comprises the following steps:
selecting hydrogen type SiO 2 /Al 2 O 3 840 g of ZSM-5 molecular sieve powder (dried before use) of 150 g of alumina15 g of pseudoboehmite, methylcellulose and sesbania powder are uniformly mixed for standby; then adding 8 g of nitric acid and 5 g of citric acid into 600 g of water to dissolve uniformly, adding calcium nitrate containing 10 g of calcium oxide to dissolve uniformly, pouring the solution into the above-mentioned mixed powder body, kneading for 35 min, extruding to form strips, placing at 20 deg.C for 12 hr, drying at 110 deg.C for 6 hr, placing into a muffle furnace, roasting at 600 deg.C for 5 hr so as to obtain the invented composite carrier (the weight percentage composition of composite carrier: ZSM-5 content 84% and Al) 2 O 3 15% calcium oxide content and 1% calcium oxide content) with a water absorption of 103%.
Preparing an impregnating solution containing 30 g of Ni by using soluble metal salt precursor basic nickel carbonate, controlling the volume of the solution to 170 ml, adding 1 g of N-dodecyl ethylenediamine sodium triacetate and 1 g of triethanolamine into the impregnating solution, stirring and dissolving uniformly, taking 170 g of composite carrier, loading the same volume of the impregnating solution on the composite carrier by adopting a rotary pot spraying method, aging for 16 hours at 25 ℃, drying for 4 hours at 100 ℃, roasting for 4 hours at 400 ℃, obtaining an oxidation catalyst, and reducing for 48 hours in a hydrogen atmosphere at 350 ℃, wherein the dispersity of Ni of the reduction catalyst is 7.6%. The peak reduction temperature of the active component under the hydrogen atmosphere was 427 ℃.
TABLE 1
Note that: * Recycle ratio refers to the volume ratio of fresh feed to reaction product for recycle
TABLE 2
Note that: * Recycle ratio refers to the volume ratio of fresh feed to reaction product for recycle
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
Note that: * Data in the table are on-line response 400 hours data.
The embodiments of the present invention are only detailed descriptions of the technical solutions of the present invention, but the present invention is not limited to the above embodiments, i.e., the present invention can be implemented without depending on the steps described in the above embodiments. In summary, any modifications to the present invention, including the substitution of materials and additives described herein, the selection of particular embodiments, etc., would be within the scope of the invention and the disclosure.
Claims (9)
1. The method for producing BTX by aromatic-rich light pyrolysis distillate oil adopts three-stage hydrogenation, wherein the first-stage hydrogenation is diene selective hydrogenation, the second-stage hydrogenation is polycyclic aromatic hydrocarbon selective hydrogenation, and the third-stage hydrogenation is selective hydrocracking; the first stage hydrogenation product has bromine number less than 25gBr 2 100g of oil, the content of polycyclic aromatic hydrocarbon in the second-stage hydrogenation product is less than 2 percent, the retention rate of aromatic hydrocarbon is more than 93 percent, the yield of the total liquid-phase product of the third-stage hydrogenation product is more than 80 percent, and the BTX yield of the liquid-phase product is more than 50 percent.
2. The process of claim 1 wherein the first stage hydrogenationThe reaction conditions of (2) are as follows: the inlet temperature of the reactor is 40-90 ℃, and the space velocity of fresh feed is 0.8-2.0 h -1 The circulation ratio is 1.0:2.0-1.0:7.0, the hydrogen-oil volume ratio is 300-1000, and the pressure is 2-8 MPa.
3. The process of claim 1, wherein the reaction conditions for the second stage hydrogenation are: the inlet temperature of the reactor is 240-350 ℃, and the space velocity of fresh feed is 0.8-2.0 h -1 The circulation ratio is 1.0:0.3-1.0:2.0, the hydrogen oil volume ratio is 500-2000, and the pressure is 2-8 MPa.
4. The process of claim 1, wherein the reaction conditions for the third stage hydrogenation are: the inlet temperature of the reactor is 380-480 ℃, and the space velocity of fresh feed is 0.6-4.0 h -1 The hydrogen oil volume ratio is 500-2000, and the pressure is 2-8 MPa.
5. The method of claim 1, wherein the aromatic-rich light cracked distillate oil: the initial boiling point is 85-170 ℃, the final boiling point is 220-280 ℃, and the raw materials consist of: sulfur content <600ug/mL, nitrogen content <300ug/mL; the aromatic hydrocarbon content is more than 90wt%.
6. The process of claim 1, wherein the catalyst used in the third stage hydrogenation comprises the following components in weight percent:
a)5％～20％Ni；
b)0.01％～5.00％CeO 2 ；
c)55.00％～89.99％ZSM-5；
d) 5% -20% of binder;
wherein the reduction temperature of the TPR hydrogen atmosphere of the catalyst used in the third stage hydrogenation is lower than 420 ℃, and the dispersity of the active component Ni is more than 7.5%, preferably 9-20%.
7. The method according to claim 6, wherein the catalyst for the third stage hydrogenation has a Ni content of 10% to 15% by weight and a CeO content of 2 The content is 0.5-3.0%, the binder content is 8-15%, and the balance is ZSM-5.
8. The process according to claim 6 or 7, wherein the catalyst used in the third stage hydrogenation comprises an alkaline earth metal oxide of 0.1% to 3.0%, preferably the alkaline earth metal oxide is calcium oxide and/or magnesium oxide.
9. The method according to claim 6, wherein the catalyst used in the third stage hydrogenation has a TPR hydrogen atmosphere reduction temperature of less than 400 ℃, more preferably the catalyst used in the third stage hydrogenation has a TPR hydrogen atmosphere reduction temperature of less than 390 ℃, and the dispersion of the active component Ni is greater than 10%, preferably 11% to 20%.
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